CN107138518A - A kind of hexavalent chromium polluted soil in-situ injection restorative procedure - Google Patents
A kind of hexavalent chromium polluted soil in-situ injection restorative procedure Download PDFInfo
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- CN107138518A CN107138518A CN201710544647.4A CN201710544647A CN107138518A CN 107138518 A CN107138518 A CN 107138518A CN 201710544647 A CN201710544647 A CN 201710544647A CN 107138518 A CN107138518 A CN 107138518A
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- hexavalent chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The present invention relates to a kind of hexavalent chromium polluted soil in-situ injection restorative procedure, according to cellular laying injector well in contaminated sites region, it will be repaiied and injected in two times in contaminated soil in order using two kinds of parenteral solutions, by principles such as absorption, chelant, reduction, precipitations, first by Cr6+It is converted into the Cr of low toxicity3+, then by Cr3+Stabilize, realize reduction Cr6+The purpose of contaminated soil environmental risk.The present invention can substantially reduce hexavalent chromium concentration and total chromium leaching concentration in soil, the environmental risk of the contaminated soil in place is reduced to acceptable level, can effectively prevent repair process pollutant from spreading using in-situ immobilization.
Description
Technical field
Field is repaired the invention belongs to heavy-metal contaminated soil, and in particular to a kind of hexavalent chromium polluted soil in-situ injection is repaiied
Compound method.
Background technology
In the production process of the industry such as leather, plating, casting, metallurgy, chemical industry, Aero-Space crome metal and chromic salts, chromium
Entered by modes such as air, waste water, solid waste, the run, drip, leak of production equipment in soil environment, soil environment is caused
Pollution.Chromium is main with Cr in soil3+And Cr6+Two kinds of forms are present, Cr in soil3+Mainly exist in the form of hydroxide, stream
Dynamic property is smaller, is low toxicity or micro- malicious form, is typically difficult to be oxidized to Cr by environmental condition6+.Research shows, Cr6+Toxicity be Cr3 +100 times, Cr6+Water is highly soluble in, with stronger migration, enrichment, Cr is easily absorbed by plants6+With Strong oxdiative thing, carcinogenic
Property and mutagenicity, plant normal growth can be influenceed, be enriched with crop body, and human body is delivered to by food chain, can be to people
Body causes harm.
Common Cr6+Contaminated soil remediation method has heavy metal pollution of soil, chemical leaching method, biological restoration, chemical reduction method, steady
Determining/solidification method etc..The total amount and leaching concentration of heavy metal pollution of soil pollutant do not change, are the transfer processes of pollutant；Change
Learning elution needs to add chemical solvent into soil, can thoroughly remove pollutant, but can change the physics and chemistry of soil simultaneously
Matter, easily causes secondary pollution；Biological restoration removes depollution by plant extraction, but this method repairing efficiency it is longer, it is necessary to
Land occupation, the normal of influence soil is used；Chemical reduction method is by Cr6+It is converted into Cr3+Restorative procedure, stabilisation/solidification
Method is a kind of method for being reduced by physico-chemical process and leaching concentration being polluted in soil.For Cr6+For contaminated soil, merely
Use electronation or stabilisation/solidification can not effectively reduce its environmental risk, in addition, major part Cr6+Contaminated soil is repaiied
It is multiple to use showering, pollutant may be caused to spread, pollute surrounding enviroment.
The content of the invention
In order to overcome the shortcomings of hexavalent chromium polluted soil heterotopic recovery technique, the invention provides a kind of hexavalent chromium polluted soil
Earth in-situ injection restorative procedure, is injected in hexavalent chromium polluted soil using special medicament, using absorption, chelant, electronation,
The principles such as precipitation, are trivalent chromium by hexavalent chrome reduction, then trivalent chromium is stabilized, to reduce hexavalent chromium concentration and trivalent in soil
Chromium leaching concentration, so that the environmental risk of hexavalent chromium polluted soil is reduced, in favor of the exploitation in soil.
The invention provides a kind of hexavalent chromium polluted soil in-situ injection restorative procedure, it comprises the following steps：
The first step, in contaminated sites region according to cellular laying in-situ injection well；
Second step, the first decoction is injected in hexavalent chromium polluted soil, is reacted 3~10 days；
3rd step, the second decoction is injected in contaminated soil, and maintenance can be checked and accepted after 7~15 days.
Wherein, first decoction is the CNT and nano zero valence iron modified using crown ether according to mass ratio 5~8
: 1 compounding is formed.
Wherein, the mass ratio of the first decoction addition and contaminated soil is (0.5~5): 100.
Wherein, the decoction of medicament second is the mixed solution of vulcanized sodium and potassium dihydrogen phosphate.
Wherein, vulcanization na concn is 0.05~1%, and biphosphate potassium concn is 0.5~2%.
Wherein, the mass ratio of second decoction and contaminated soil is (5~20): 100.
The present invention also provides a kind of hexavalent chromium polluted soil in-situ parenteral solution, and it includes the carbon nanometer modified using crown ether
Pipe and nano zero valence iron are formed according to the compounding of mass ratio 5~8: 1.
The present invention also provides a kind of hexavalent chromium polluted soil in-situ parenteral solution, and it includes mixing for vulcanized sodium and potassium dihydrogen phosphate
Solution is closed, vulcanization na concn is 0.05~1%, and biphosphate potassium concn is 0.5~2%.
It is of the invention that there is advantages below and effect compared with existing recovery technique：
(1) present invention is repaired using in-situ injection medicament method to hexavalent chromium polluted soil, and reduction showering can
The risk that pollutant can be caused to spread, meanwhile, reduce rehabilitation cost；
Both materials of (2) first decoctions are innocuous substance, will not cause secondary pollution to soil, have gathered absorption
With reduction two major features, improve Cr VI and reducing agent contact probability, lift repairing effect, in addition, the compounding product no matter
Alkalescence or sour environment are respectively provided with stronger reproducibility, and repair process need not adjust pH；
(3) second decoctions are formed by reducing agent and precipitating reagent compounding, can both reduce the unreduced Cr in part6+, again may be used
By Cr3+Indissoluble material is converted into, Cr is reduced3+Stripping property, and reduce changes in environmental conditions and cause Cr3+It is converted into Cr6+Possibility
Property.
Brief description of the drawings
Fig. 1 is ultraviolet-absorbable spectrogram for the CNT that crown ether is modified；
Fig. 2 is the transmission electron microscope figure of the CNT before crown ether is modified；
Fig. 3 is the transmission electron microscope figure of the CNT after crown ether is modified.
Embodiment
The invention provides a kind of hexavalent chromium polluted soil in-situ injection restorative procedure, comprise the following steps：
The first step, in contaminated sites region according to cellular laying in-situ injection well；
Second step, the first decoction is injected in hexavalent chromium polluted soil, is reacted 3~10 days；
3rd step, the second decoction is injected in contaminated soil, and maintenance can be checked and accepted after 7~15 days.
First decoction is that the CNT and nano zero valence iron modified using crown ether are multiple according to mass ratio 5~8: 1
With into, the CNT and nano zero valence iron of modification are put into water jointly, stirred 10 minutes, it is described to repair as outstanding mixed liquid
The CNT of decorations and the quality sum of nano zero valence iron and the mass ratio of water are 1~2: 1, the first decoction addition with
The mass ratio of contaminated soil is (0.5~5): 100.
The decoction of medicament second is the mixed solution of vulcanized sodium and potassium dihydrogen phosphate, is by vulcanized sodium and potassium dihydrogen phosphate
Configuration is dissolved in water to form, vulcanization na concn be 0.05~1%, biphosphate potassium concn be 0.5~2%, the second decoction with
The mass ratio of contaminated soil is (5~20): 100.
CNT is with very high mechanical property, its unique Electronic Performance, big draw ratio, high chemically stable
Property and big specific surface area extensive use is all obtained in many fields, absorb take out water in heavy metal contaminants in terms of
Through conducting extensive research.
CNT has very big specific surface area, there is absorption effect well to inorganic non-metallic ion, heavy metal ion
Really.Further, since CNT has very big specific surface area, there are very strong suction-operated, organic substance to organic compound
Change its surface properties with CNT interaction, be coated on carbon nano tube surface, the present invention is considered as and trivalent chromium gold
Category has the organic compound modified carbon nano tube surface of more preferable coordination property, and progress is function modified, preferably improves to trivalent chromium
Suction-operated.
The organic chemical modification of CNT is segmented into two types, and one kind is covalently chemical functionalized, and one kind is non-co-
Valency chemical modification.The side wall of CNT is made up of the graphite of lamellar structure, the sp of carbon atom2Hydridization formation is highly delocalized
Pi-electron, these pi-electrons can be used to be combined by π-π non-covalent bond effects with other compounds containing pi-electron, obtain
To the CNT of functionalization, this organic decoration method will not cause structure to destroy CNT in itself, obtain structure guarantor
The functional carbon nanotubes held.
In research process, it has been found that the big pi-electron conjugated system of CNT makes it easily assemble bunchy, it is difficult to shape
Into homogeneous film, acidifying modification is carried out to CNT, prevents it from assembling bunchy, as homogeneous film, makes to repair to greatest extent
The organic matter of decorations can fully be combined with trivalent chromic ion.
It as chelating agent is a kind of organic substance of effectively chelated mineral cation that crown ether, which is, and it can be used as one
Plant strong ligand and be applied to various transition metal, the crown compound that someone is prepared by double (methylol) phenol of 2,6-, this
Crown compound of the prior art is used for reference in invention, finds a kind of crown compound by studying, it has to trivalent chromic ion
Stable chelation, forms stable compound.In the present invention, the crown ether chemical combination prepared by double (methylol) phenol of 2,6-
Thing forms stable closed loop parcel trivalent chromic ion, forms stable compound, is conducive to the absorption of trivalent chromic ion.
The preparation method of the CNT of the crown ether modification is as follows：
The first step, the acidifying of CNT often takes 5g multi-walled carbon nanotubes to be placed in 50ml hydrochloric acid and sulfuric acid mixed system
In, the volume ratio of hydrochloric acid and sulfuric acid is 2: 1, and hydrochloric acid uses 37% concentrated hydrochloric acid, and sulfuric acid uses 98% concentrated sulfuric acid,
Ultrasound environments are shaken, and multi-walled carbon nanotube is uniformly dispersed in nitration mixture, are heated to 40 DEG C of stirring reactions 4 hours, are cooled to room
Temperature, plus 5 times of nitration mixture volumes deionized water dilute solution, filtering, the CNT after acidifying cleans 3 times with deionized water, gone out
Remove acid remaining in CNT, product 70 DEG C of dryings 24 hours under 0.1Mpa vacuum environments obtain the smooth solid in surface；
Second step, coronal ether compound prepared by 10g is dissolved in DMF 70ml, ultrasonic oscillation
25 minutes, fully dissolving, filtering obtained yellow solution, the multi-walled carbon nanotube of 8g acidifyings prepared by the first step was added, at 35 DEG C
Under the conditions of ultrasonic vibration 1 hour, dissolve CNT, obtain the CNT of homogeneous phase solution, as organic decoration.
The preparation method of crown ether is as follows：
The first step, by 1mol 2, double (methylol) phenol of 6- and 1mol 2,2- dimethylpropanes are dissolved in 50ml dichloromethanes
In alkane solution, triflate catalyst 0.05mol is added, reaction 2 hours is stirred at room temperature, filtering, solution steams in rotation
Send out and concentrated on instrument, obtain solid fraction compound 1, i.e. (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) methanol；
Second step, 1mol (2,2,6- trimethyl -4H-1, the 3- benzo dioxin -8- methyl) methanol for taking the first step to obtain
It is dissolved in 40ml dichloromethane solutions, adds 1mol pyridine chlorochromates and carry out acetalation, reaction 1.5 is stirred at room temperature small
When, filtering, solution is concentrated on a rotary evaporator, obtains solid fraction compound 2, i.e. (2,2,6- trimethyl -4H-1,3- benzos two
Dislike English -8- methyl) formaldehyde；
3rd step, (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) formaldehyde prepared by 1mol second steps
It is dissolved in 65ml n-hexanes, leads to bromination hydrogen, throughput 80ml per minute realizes deprotection and Benzylphosphonium Bromide, and filtering is molten
Liquid is concentrated on a rotary evaporator, obtains solid fraction compound 3, i.e. 3- (bromomethyl) -2- hydroxyl -5- benzaldehydes；
4th step, takes 1mol O, and O '-bis- (2- hydroxy ethoxies) benzene is dissolved in 50ml tetrahydrofuran solutions, is subsequently added
2.2mol3- (bromomethyl) -2- hydroxyl -5- benzaldehydes and 0.05mol sodium hydrides, are stirred at room temperature 30 minutes, filtering, molten
Liquid is concentrated on a rotary evaporator, and acquisition solid fraction compound 4, i.e., 3,3 '-((((1,2- phenylene two (oxo)) two (ethane -2,
1- diyls)) two (oxos)) two (methylene)) two (2- hydroxy-5-methyl base benzene (first) aldehyde)；
5th step, the compound 4 for taking the steps of 1mol the 4th to prepare is dissolved in 110ml ethanol, is subsequently added 2.5mol 1- pyrene first
Amine hydrochlorate, is heated to 60 DEG C and stirs 1 hour, be down to room temperature, 0 DEG C static 2 hours, filter, solution is dense on a rotary evaporator
Contracting, obtains solid fraction compound 5, as shown in following formula 1, i.e. 2- ((E)-(((3a1,5a1- dihydropyrene -1- bases) methyl) imino group) first
Base) -6- ((2- (2- (2- ((2- hydroxy-5-methyl bases -3- ((E)-((pyrene -1- ylmethyls) imino group) methyl) benzyl) oxo)
Ethyoxyl) phenoxy group) ethyoxyl) methyl) -4- methylphenols.
The characteristics of nano zero valence iron has extremely strong reproducibility and is swift in response, can compared with common iron powder and iron filings
Significantly more efficient heavy-metal ion removal, can be very good hexavalent chrome reduction into trivalent chromium, but in use can shape
Into FeOOH and trivalent chromium formation alloy hydroxide, increase electronics is transferred to the resistance of Cr VI from Zero-valent Iron, makes rate of reduction
Reduction.In the present invention by zeroth order iron powder and the CNT of organic decoration, zeroth order iron powder by Cr VI heavy metal also
It is former into after trivalent chromium, run through CNT and adsorbed and further by the organic group chelating above it, make three
Valency chromium will not realize Zero-valent Iron reduction of hexavalent chromium to greatest extent with FeOOH formation alloy hydroxides.
The nano zero valence iron used can use commercially available, it would however also be possible to employ Physical, chemical method and bioanalysis are appointed
Nano zero valence iron prepared by a kind of what method.
Relative to traditional dystopy heavy metal-polluted soil restorative procedure, in-situ injection reparation is used in the present invention, closely
Year based technique for in-situ remediation is increasingly taken seriously.But compared with showering technology, using in-situ injection reparation, single repaiies
Redoubling is not thorough, and to reach even preferably repairing effect identical with showering technology, the present invention is using first group of injection
Repair after liquid, liquid is repaired in further second group of injection of injection, and first group of parenteral solution can shorten repair time, second group of note
Penetrate and repair the completeness that liquid ensure that reparation, the in-situ injection of the present invention is repaired quick perfect completion repair.
The present invention is described in further detail with reference to the accompanying drawings and detailed description, but protection scope of the present invention
It is not limited to the content.
The preparation of the crown ether of embodiment 1
By 1mol 2, double (methylol) phenol of 6- and 1mol 2,2- dimethylpropanes are dissolved in 50ml dichloromethane solutions
In, triflate catalyst 0.05mol is added, reaction 2 hours is stirred at room temperature, is filtered, solution is on a rotary evaporator
Concentration, obtains (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- methyl) methanol；Take 1mol (2,2, the 6- front threes of acquisition
Base -4H-1,3- benzo dioxin -8- methyl) methanol is dissolved in 40ml dichloromethane solutions, and add 1mol pyridine chlorochromates and enter
Row acetalation, is stirred at room temperature reaction 1.5 hours, and filtering, solution is concentrated on a rotary evaporator, obtains (2,2,6- front threes
Base -4H-1,3- benzo dioxin -8- methyl) formaldehyde；By 1mol (2,2,6- trimethyl -4H-1,3- benzo dioxin -8- first
Base) formaldehyde is dissolved in 65ml n-hexanes, leads to bromination hydrogen, and throughput 80ml per minute realizes deprotection and Benzylphosphonium Bromide,
Filtering, solution is concentrated on a rotary evaporator, obtains 3- (bromomethyl) -2- hydroxyl -5- benzaldehydes；Take 1mol O, O '-bis- (2-
Hydroxy ethoxy) benzene, it is dissolved in 50ml tetrahydrofuran solutions, is subsequently added 2.2mol3- (bromomethyl) -2- hydroxyl -5- benzaldehydes
And 0.05mol sodium hydrides, it is stirred at room temperature 30 minutes, filters, solution is concentrated on a rotary evaporator, acquisition 3,3 '-
((((1,2- phenylene two (oxo)) two (ethane -2,1- diyls)) two (oxos)) two (methylene)) two (2- hydroxy-5-methyl bases
Benzene (first) aldehyde)；Take 1mol 3,3 '-((((1,2- phenylene two (oxo)) two (ethane -2,1- diyls)) two (oxos)) two (Asia
Methyl)) two (2- hydroxy-5-methyl base benzene (first) aldehyde) are dissolved in 110ml ethanol, are subsequently added 2.5mol 1- pyrene methylamine hydrochlorides,
It is heated to 60 DEG C to stir 1 hour, is down to room temperature, 0 DEG C static 2 hours, filter, concentrate on a rotary evaporator, obtains solid production
Thing, 2- ((E)-(((3a1,5al- dihydropyrene -1- bases) methyl) imino group) methyl) -6- ((2- (2- (2- ((2- hydroxy-5-methyls
Base -3- ((E)-((pyrene -1- ylmethyls) imino group) methyl) benzyl) oxo) ethyoxyl) phenoxy group) ethyoxyl) methyl) -4-
Methylphenol.
The compound1H NMR datas are as follows：
1H-NMR (300MHz, DMSO) δ 8.80-8.71 (m, 2H), 8.31 (m, 1H), 8.23 (m, 1H), 8.13-8.03
(m, 2H), 8.04 (m, 1H), 7.78 (m, 1H), 7.70 (m, 1H), 7.62 (m, 1H), 7.54 (m, 1H), 7.22 (m, 1H), 7.09
(m, 1H), 7.05 (m, 1H), 6.99-6.83 (m, 4H), 6.78-6.68 (m, 2H), 6.57 (s, 1H), 6.09 (s, 1H), 5.84
(s, 2H), 5.80 (s, 1H), 5.31 (s, 4H), 4.80 (s, 4H), 4.31 (t, J=8.4Hz, 4H), 3.77 (t, J=8.4Hz,
4H), 3.66 (s, 2H), 2.63 (s, 2H), 2.36 (s, 3H)；ES-LCMS m/z 923.4(M+H).
The CNT of the crown ether of embodiment 2 modification
5g multi-walled carbon nanotubes are taken to be placed in 50ml hydrochloric acid and sulfuric acid mixed system, the volume ratio of hydrochloric acid and sulfuric acid is 2:
1, hydrochloric acid uses 37% concentrated hydrochloric acid, and sulfuric acid uses 98% concentrated sulfuric acid, and ultrasound environments concussion makes multi-wall carbon nano-tube
Pipe is uniformly dispersed in nitration mixture, is heated to 40 DEG C of stirring reactions 4 hours, is cooled to room temperature, plus 5 times of nitration mixture volumes deionized water
Dilute solution, filtering, the CNT after acidifying is cleaned 3 times with deionized water, and remaining acid in CNT of going out, product exists
The lower 70 DEG C of dryings of 0.1Mpa vacuum environments 24 hours, obtain the smooth solid in surface；Coronal etherificate prepared by 10g embodiments 1
Compound is dissolved in DMF 70ml, ultrasonic oscillation 25 minutes, fully dissolving, and filtering obtains yellow solution,
The multi-walled carbon nanotube of 8g acidifyings prepared by the first step is added, ultrasonic vibration 1 hour, makes CNT molten under the conditions of 35 DEG C
Solution, obtains the CNT of homogeneous phase solution, as organic decoration.
UV-Vis spectra is analyzed
The coronal ether compound and the compound-modified many wall carbon of the crown ether of embodiment 2 for weighing the preparation of embodiment 1 respectively are received
Mitron, is dissolved in tetrahydrofuran solution, and ultrasonic vibration obtains uniform solution, uses Japanese Hitachi companies
330Spectrophotometer tests two tetrahydrofuran solutions and obtains uv-visible absorption spectroscopy respectively.
Fig. 1 shows crown ether organic compound and its ultraviolet-visible of CNT modified in tetrahydrofuran solution
Spectrum.
From figure as can be seen that a show embodiment 1 prepare coronal ether compound occur 430nm at significantly it is very wide
Characteristic absorption peak, this is the π-π * electron transitions of the compound, b show π after the compound-modified multi-walled carbon nanotube of crown ether-
The absworption peak of π * electron transitions appears in 457nm, with crown ether compound phase ratio, moves 27nm, because coronal etherificate
Compound and CNT formation conjugated system, it is overlapping to there is local electronics, moves absworption peak.
Tem study
Weigh respectively crown ether modification prepared by a small amount of embodiment 2 CNT and it is commercially available it is unmodified before carbon receive
Mitron, is dissolved in tetrahydrofuran solution, and ultrasonic vibration is then dropped on copper mesh, drying, uses Japanese Hitachi companies
Microscopic pattern change between CNT after the modification of 8000 transmission electron microscope observations and the CNT before modification.
Analyze CNT electromicroscopic photograph Fig. 2 and Fig. 3 before and after the organic compound modified CNT of crown ether
As can be seen that the caliber of unmodified multi-walled carbon nanotube is small, tube wall is smooth, and after modification, the pipe of multi-walled carbon nanotube
Footpath substantially becomes big, and caliber is thickening, and due to there is the modification of the parcel of coronal ether compound, appearance is uneven.
The preparation method of nano zero-valence iron powder uses the method that professor Li Fashen provides, or using commercially available.
Using the Li Fashen methods taught specifically, using Gas Evaporation Method, evaporation cavity first is evacuated down into 1 × 10- 5Torr, is subsequently passed Ar gases, and purity is 99.99%, and using refractory metal molybdenum as heating source, metallic iron is in evaporation cavity
Evaporation, evaporation is passed through N after terminating2Gas, is passivated processing, obtains nano zero valence iron.
For examination soil：
Object is certain hexavalent chromium polluted soil in Electroplate Factory former address place, and the place soil hexavalent chromium concentration is 25~365mg/
Kg, average value is 54mg/kg.
Restorative procedure：
It is as follows that the present invention repairs the contaminated soil step：
(1) in contaminated sites region according to cellular laying in-situ injection well, Polluted area 100m2, every mouthful of injector well shadow
It is 25m to ring scope2, Polluted area is interior to lay 4 mouthfuls of monitoring wells；
(2) the first decoction is reacted into 5 days, described first according in the 3% hexavalent chromium polluted soil of injection of contaminated soil amount
The CNT and nano zero-valence iron powder that decoction is modified by the crown ether for preparing embodiment 2 according to mass ratio 5: 1 ratio
It is put into water, stirs 10 minutes, as outstanding mixed liquid, injects in contaminated soil, the CNT and nano zero-valence of crown ether modification
The quality sum of iron powder and the mass ratio of water are 1: 1；
(3) the second decoction is conserved 10 days, second decoction according in 12% injection contaminated soil of contaminated soil amount
Vulcanized sodium and potassium dihydrogen phosphate example in mass ratio are dissolved in water, the configuration that stirs is formed, vulcanization na concn is 0.5%,
Potassium dihydrogen phosphate is 1%.
It is divided into four groups：First group use the embodiment of the present invention in the first medicament and second medicament, according to above-mentioned reparation
Soil method carries out in-situ injection reparation, and second group carries out in-situ injection reparation using with first group of identical mode, and difference exists
In the CNT that the organic substance modification in the first medicament of the invention is replaced using commercially available CNT, remaining situation is complete
Identical, the 3rd group is injected in contaminated soil only with the second decoction according to the 12% of contaminated soil amount, continuous maintenance 15 days, the 4th
Group is without any medicament.Four groups of sample times are identical with analysing content.
Analysis method
Total chromium and content of 6-valence Cr ions in determining soil extract at the 5th day and the 15th day respectively, total chromium content in soil analysis
Leaching leaching method uses horizontal vibration method HJ557-2010 in method reference EPA3060A, soil《Solid waste is soaked
Go out toxicity leaching method, horizontal vibration method》, the total chromium of leachate determines with ICP-AES, Cr VI diphenylcarbazide light splitting light
Degree method is determined.
Medicament is repaired within 5th day to the repairing effect of chromium-polluted soil, 1 is the results are shown in Table.
The 5th day repairing effect to chromium-polluted soil of table 1
As it can be seen from table 1 comparing first group and the 4th group, the first reparation decoction provided using the present invention is repaiied
It is multiple, the total cr content and Cr of leachate after reparation6+Content is significantly reduced compared with native soil, and is compared and repaiied using present invention offer first
First group and second without the CNT for carrying out organic substance modification of the CNT of the organic substance modification of multiple decoction
Group situation, the CNT repaired using organic substance of the present invention is disposed more due to the chelating coating function of organic substance
Cr3+Ion, makes the total cr content after reparation and Cr6+Content is significantly lower than second group.Compare first group and the 3rd group, in phase
In same repair time, it is substantially more preferable that the first decoction ratio provided using the present invention carries out treatment effect using vulcanized sodium.
Medicament is repaired within 15th day to the repairing effect of chromium-polluted soil, 2 are the results are shown in Table.
The 15th day repairing effect to chromium-polluted soil of table 2
In-situ injection reparation is carried out from table 2 it can be seen that coordinating using the first decoction of the invention and the second decoction, final
The total cr content and Cr of leachate after reparation6+Content is more preferable using the effect of common CNT compared with the first decoction
Described above is only the preferred embodiments of the present invention, is not intended to limit the invention；Others are any not to depart from this
Modification, replacement, simplification, improvement that the principle and concept thereof of invention are made etc., should be regarded as equivalent substitute mode, in this hair
Within bright protection domain.
Claims (8)
1. a kind of hexavalent chromium polluted soil in-situ injection restorative procedure, it is characterised in that：Comprise the following steps,
The first step, in contaminated sites region according to cellular laying in-situ injection well；
Second step, the first decoction is injected in hexavalent chromium polluted soil, is reacted 3~10 days；
3rd step, the second decoction is injected in contaminated soil, and maintenance can be checked and accepted after 7~15 days.
2. hexavalent chromium polluted soil in-situ injection restorative procedure as claimed in claim 1, it is characterised in that：First decoction
To be formed using the CNT and nano zero valence iron of crown ether modification according to the compounding of mass ratio 5~8: 1.
3. hexavalent chromium polluted soil in-situ injection restorative procedure as claimed in claim 1 or 2, it is characterised in that：Described first
The mass ratio of decoction addition and contaminated soil is (0.5~5): 100.
4. the hexavalent chromium polluted soil in-situ injection restorative procedure as described in claims 1 to 3, it is characterised in that：The medicament
Second decoction is the mixed solution of vulcanized sodium and potassium dihydrogen phosphate.
5. the hexavalent chromium polluted soil in-situ injection restorative procedure as described in Claims 1-4, it is characterised in that：Vulcanized sodium is dense
Spend for 0.05~1%, biphosphate potassium concn is 0.5~2%.
6. the hexavalent chromium polluted soil in-situ injection restorative procedure as described in claim 1 to 5, it is characterised in that：Described second
The mass ratio of decoction and contaminated soil is (5~20): 100.
7. a kind of hexavalent chromium polluted soil in-situ parenteral solution, it is characterised in that：Including using crown ether modify CNT and
Nano zero valence iron is formed according to the compounding of mass ratio 5~8: 1.
8. a kind of hexavalent chromium polluted soil in-situ parenteral solution, it is characterised in that：Mixing including vulcanized sodium and potassium dihydrogen phosphate is molten
Liquid, vulcanization na concn is 0.05~1%, and biphosphate potassium concn is 0.5~2%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710544647.4A CN107138518A (en) | 2017-07-06 | 2017-07-06 | A kind of hexavalent chromium polluted soil in-situ injection restorative procedure |
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| CN113634589A (en) * | 2021-06-07 | 2021-11-12 | 广东石油化工学院 | Combined remediation method for composite contaminated soil by using iron-carbon-based material |
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| CN113634589A (en) * | 2021-06-07 | 2021-11-12 | 广东石油化工学院 | Combined remediation method for composite contaminated soil by using iron-carbon-based material |
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